- Mechanochemical Transformation of CF3 Group: Synthesis of Amides and Schiff Bases
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We communicate two mild, solvent-free mechanochemical coupling transformations of CF3 group with nitro compounds into amides or Schiff bases employing Ytterbia as a catalyst. This process proceeds via C?F bond activation, accompanied with utilisation of Si-based reductants/oxygen scavengers – reductants of the nitro group. The scope and limitations of the disclosed methodologies are thoroughly studied. To the best of our knowledge, this work is the first example of mechanical energy promoted transformation of the inert CF3 group into other functionalities. (Figure presented.).
- Mkrtchyan, Satenik,Jakubczyk, Micha?,Lanka, Suneel,Yar, Muhammad,Ayub, Khurshid,Shkoor, Mohanad,Pittelkow, Michael,Iaroshenko, Viktor O.
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supporting information
p. 5448 - 5460
(2021/10/19)
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- High Turnover Pd/C Catalyst for Nitro Group Reductions in Water. One-Pot Sequences and Syntheses of Pharmaceutical Intermediates
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Commercially available Pd/C can be used as a catalyst for nitro group reductions with only 0.4 mol % Pd loading. The reaction can be performed using either silane as a transfer hydrogenating agent or simply a hydrogen balloon (μ1 atm pressure). With this technology, a series of nitro compounds was reduced to the desired amines in high chemical yields. Both the catalyst and surfactant were recycled several times without loss of reactivity.
- Gallou, Fabrice,Li, Xiaohan,Lipshutz, Bruce H.,Takale, Balaram S.,Thakore, Ruchita R.
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supporting information
p. 8114 - 8118
(2021/10/25)
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- Selective Carbon-Carbon Bond Amination with Redox-Active Aminating Reagents: A Direct Approach to Anilines?
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Amines are among the most fundamental motifs in chemical synthesis, and the introduction of amine building blocks via selective C—C bond cleavage allows the construction of nitrogen compounds from simple hydrocarbons through direct skeleton modification. Herein, we report a novel method for the preparation of anilines from alkylarenes via Schmidt-type rearrangement using redox-active amination reagents, which are easily prepared from hydroxylamine. Primary amines and secondary amines were prepared from corresponding alkylarenes or benzyl alcohols under mild conditions. Good compatibility and valuable applications of the transformation were also displayed.
- Qiu, Xu,Wang, Yachong,Su, Lingyu,Jin, Rui,Song, Song,Qin, Qixue,Li, Junhua,Zong, Baoning,Jiao, Ning
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p. 3011 - 3016
(2021/09/13)
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- Nucleophilic aromatic substitution of unactivated fluoroarenes enabled by organic photoredox catalysis
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Nucleophilic aromatic substitution (SNAr) is a classical reaction with well-known reactivity toward electron-poor fluoroarenes. However, electron-neutral and electron-rich fluoro(hetero)arenes are considerably underrepresented. Herein, we present a method for the nucleophilic defluorination of unactivated fluoroarenes enabled by cation radical-accelerated nucleophilic aromatic substitution. The use of organic photoredox catalysis renders this method operationally simple under mild conditions and is amenable to various nucleophile classes, including azoles, amines, and carboxylic acids. Select fluorinated heterocycles can be functionalized using this method. In addition, the late-stage functionalization of pharmaceuticals is also presented. Computational studies demonstrate that the site selectivity of the reaction is dictated by arene electronics.
- Nicewicz, David A.,Pistritto, Vincent A.,Schutzbach-Horton, Megan E.
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supporting information
p. 17187 - 17194
(2020/11/02)
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- AMINATION AND HYDROXYLATION OF ARYLMETAL COMPOUNDS
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In one aspect, the present disclosure provides methods of preparing a primary or secondary amine and hydroxylated aromatic compounds. In some embodiments, the aromatic compound may be unsubstituted, substituted, or contain one or more heteroatoms within the rings of the aromatic compound. The methods described herein may be carried out without the need for transition metal catalysts or harsh reaction conditions.
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Paragraph 0098; 0134; 0135; 0183
(2018/03/25)
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- ORGANIC REACTIONS CARRIED OUT IN AQUEOUS SOLUTION IN THE PRESENCE OF A HYDROXYALKYL(ALKYL)CELLULOSE OR AN ALKYLCELLULOSE
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The present invention relates to a method of carrying out an organic reaction in aqueous solution in the presence of a hydroxyalkyl(alkyl)cellulose or an alkylcellulose.
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Page/Page column 251; 252
(2017/08/21)
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- Rapid heteroatom transfer to arylmetals utilizing multifunctional reagent scaffolds
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Arylmetals are highly valuable carbon nucleophiles that are readily and inexpensively prepared from aryl halides or arenes and widely used on both laboratory and industrial scales to react directly with a wide range of electrophiles. Although C-C bond formation has been a staple of organic synthesis, the direct transfer of primary amino (-NH2) and hydroxyl (-OH) groups to arylmetals in a scalable and environmentally friendly fashion remains a formidable synthetic challenge because of the absence of suitable heteroatom-transfer reagents. Here, we demonstrate the use of bench-stable N-H and N-alkyl oxaziridines derived from readily available terpenoid scaffolds as efficient multifunctional reagents for the direct primary amination and hydroxylation of structurally diverse aryl- and heteroarylmetals. This practical and scalable method provides one-step synthetic access to primary anilines and phenols at low temperature and avoids the use of transition-metal catalysts, ligands and additives, nitrogen-protecting groups, excess reagents and harsh workup conditions.
- Gao, Hongyin,Zhou, Zhe,Kwon, Doo-Hyun,Coombs, James,Jones, Steven,Behnke, Nicole Erin,Ess, Daniel H.,Kürti, László
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p. 681 - 688
(2017/06/30)
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- 4,5-dihydropyrazolo [3,4-c] pyridine-2-one spiro derivatives, its preparation method and application
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Disclosed are a spirocyclic derivative of 4,5-dihydropyrazolo[3,4-c]pyridine-2-one as represented by general formula (I), preparation method and use thereof, the definition of each substituent in the compound of general formula (I) being the same as the definition in the description.
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Paragraph 0640-0645
(2016/10/08)
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- Novel bicyclic heterocyclic compounds, process for their preparation and compositions containing them
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The present invention provides, among other things, new bicyclo heterocyclic compounds, compositions comprising these heterocyclic compounds, methods of making the heterocyclic compounds, and methods of using these heterocyclic compounds for treating a variety of conditions and disease states associated with, for example, cellular proliferation, inflammation, glycosidase expression, or the low expression of Perlecan.
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Page/Page column 77
(2008/06/13)
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- Electrophilic aromatic fluorination with fluorine: meta-Directed fluorination of anilines
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Anilines are mainly or selectively fluorinated in the meta-position with F2 when dissolved in triflic acid, sometimes in the presence of small quantities of antimony pentafluoride. The regioselectivity is increased when an electron-donating substituent is present at the para-position.
- Alric,Marquet,Billard,Langlois
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p. 661 - 667
(2007/10/03)
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- Analogues of camptothecin, their use as medicaments and the pharmaceutical compositions containing them
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A compound of the formula wherein the substituents are defined as in the specification which compounds are useful in the treatment of cancer.
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- New analogues of camptothecin, their use as medicaments and the pharmaceutical compositions containing them
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A compound of the formula wherein the substituents are defined as in the specification which compounds are useful in the treatment of cancer.
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- Indole derivatives as mcp-1 receptor antagonists
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A compound of formula (I) wherein: R1 is hydrogen, halo or methoxy; R2 is hydrogen, halo, methyl, ethyl or methoxy; R3 is a halo group or a trifluoromethyl group; R4 is a halo group or a trifluoromethyl group; R5 is hydrogen or halo; R6 is hydrogen or halo; provided that when R5 and R6 are both hydrogen, and one of R3 or R4 is chloro or fluoro, then the other is not chloro or fluoro; or a pharmaceutically acceptable salt or prodrug thereof. These compounds have useful activity for the treatment of inflammatory disease, specifically in antagonising an MCP-1 mediated effect in a warm-blooded animal such as a human being.
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- SUBSTITUTED QUINAZOLINE DERIVATIVES AND THEIR USE AS INHIBITORS
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The use of a compound of formula (I) 1 or a salt, ester or amide thereof; where X is O, or S, S(O) or S(O)2, or NR6 where R6 is hydrogen or C1-6 alkyl,; R5 is an optionally substituted 5-membered heteroaromatic ring, R1, R2 ,R3, R4 are independently selected from various specified moieties, in the preparation of a medicament for use in the inhibition of aurora 2 kinase. Certain compounds are novel and these, together with pharmaceutical compositions containing them are also described and claimed
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- Effect of ring fluorination on the pharmacology of hallucinogenic tryptamines
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A series of fluorinated analogues of the hallucinogenic tryptamines N,N-diethyltryptamine (DET), 4-hydroxy-N,N-dimethyltryptamine (4-OH-DMT, psilocin), and 5-methoxy-DMT was synthesized to investigate possible explanations for the inactivity of 6-fluoro-DET as a hallucinogen and to determine the effects of fluorination on the molecular recognition and activation of these compounds at serotonin receptor subtypes. The target compounds were evaluated using in vivo behavioral assays for hallucinogen-like and 5-HT(1A) agonist activity and in vitro radioligand competition assays for their affinity at 5-HT(2A), 5-HT(2C), and 5-HT(1A) receptor sites. Functional activity at the 5-HT(2A) receptor was determined for all compounds. In addition, for some compounds functional activity was determined at the 5-HT(1A) receptor. Hallucinogen-like activity, evaluated in the two-lever drug discrimination paradigm using LSD-trained rats, was attenuated or abolished for all of the fluorinated analogues. One of the tryptamines, 4-fluoro-5-methoxy-DMT (6), displayed high 5-HT(1A) agonist activity, with potency greater than that of the 5-HT(1A) agonist 8-OH-DPAT. The ED50 of 6 in the two-lever drug discrimination paradigm using rats trained to discriminate the 5-HT(1A) agonist LY293284 was 0.17μmol/kg, and the K(i) at [3H]8-OH-DPAT-labeled 5-HT(1A) receptors was 0.23 nM. The results indicate that fluorination of hallucinogenic tryptamines generally has little effect on 5-HT(2A/2C) receptor affinity or intrinsic activity. Affinity at the 5-HT(1A) receptor was reduced, however, in all but one example, and all of the compounds tested were full agonists but with reduced functional potency at this serotonin receptor subtype. The one notable exception was 4-fluoro-5-methoxy-DMT (6), which had markedly enhanced 5-HT(1A) receptor affinity and functional potency. Although it is generally considered that hallucinogenic activity results from 5-HT(2A) receptor activation, the present results suggest a possible role for involvement of the 5-HT(1A) receptor with tryptamines.
- Blair,Kurrasch-Orbaugh,Marona-Lewicka,Gumbay,Watts,Barker,Nichols
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p. 4701 - 4710
(2007/10/03)
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- Camptothecin analogues, preparation methods therefor, use thereof as drugs, and pharmaceutical compositions containing said analogues
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A camptothecin analog characterized in that the hydroxy lactone of the camptothecin is a β-hydroxy lactone or the corresponding β-hydroxyacid, resulting from the opening of said lactone, or a derivative of said β-hydroxyacid, or a Pharmaceutically acceptable salt thereof, is disclosed. In particular, compounds of formulae (I) and (II) are disclosed. Methods for preparing the compounds of formulae (I) and (II), pharmaceutical compositions containing said containing said compounds, and their use, particularly as topoisomerase inhibitors and antitumoral drugs, are also disclosed.
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- Benzoylurea compounds and pesticides containing them
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A benzoylurea compound having the formula: STR1 wherein each of X1 and X2 is a hydrogen atom, a halogen atom or a methyl group, provided that X1 and X2 are not simultaneously hydrogen atoms, Y is independently a
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- 4-Methyl-5-(unsubstituted and substituted phenoxy)-6-methoxy-8-(aminoalkylamino)quinolines
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Compounds of the class including 4-methyl-5-(unsubstituted and substitutedhenoxy)-6-methoxy-8-(aminoalkylamino)quinolines as the free bases and pharmaceutically acceptable acid amine salts are described. The compounds are highly effective antimalarial agents which possess, surprisingly, both tissue schizonticidal (radical curative) and blood schizonticidal (suppressive) activity. In addition, these drugs have significantly better therapeutics indices than primaquine which is the current tissue schizonticidal drug of choice. Primaquine possesses no useful blood schizonticidal activity at tolerated dose levels.
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- The Kinetics of the Reactions of Picryl Chloride with Some Substituted Anilines. Part 6. 4-Substituted and 3,4-Disubstituted Anilines
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Arrhenius parameters have been measured for the reactions of picryl chloride with the following substituted anilines in acetonitrile: 4-X- (X = F, Cl, Br, I, Me, or OMe); 3,4-X2- (X = Cl, Br, Me, or OMe); 4-X-3-nitro- (X = F, Cl, or Me); 3-X-4-methoxy- (X = F, Cl, Br, or I); 3-fluoro-4-nitro-; and 3,4,5-trimethoxy-aniline.In the 3,4-disubstituted series the effect of two methyl groups on the free energy of activation is strictly additive, but for the rest the measured rate constants are greater than those calculated on the assumption of additivity.The results are rationalized in terms of the positions of the transition state on the reaction co-ordinate.
- Emokpae, Thomas A.,Eguavoen, Osa,Khalil-Ur-Rahman,Hirst, Jack
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p. 832 - 834
(2007/10/02)
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